Method of treating a wood surface with linear heat-hardenable copolymerizate

ABSTRACT

IN WHICH R1 is selected from the group consisting of hydrogen and a methyl group, and R2 is an alkyl group having one to four carbon atoms, 2 TO 15 MOLE PERCENT OF AT LEAST ONE COMPOUND SELECTED FROM THE GROUP CONSISTING OF MALEIC ANHYDRIDE AND ITACONIC ACID ANHYDRIDE, AND 4 TO 15 MOLE PERCENT OF AT LEAST ONE COMPOUND SELECTED FROM THE GROUP CONSISTING OF ACRYLIC ACID GLYCIDYL ESTER AND METHACRYLIC ACID GLYCIDYL ESTER.   This invention relates to a linear heat-hardenable copolymerizate, and to a method of treating a wood surface with a foil of the said copolymerizate, the copolymerizate having a limiting viscosity of Eta 0.7 to 3.0 (100 ml . g 1) measured in toluene at 20* C., and comprising 70 TO 94 MOLE PERCENT OF A COMPOUND SELECTED FROM THE GROUP CONSISTING OF STYRENE OR AT LEAST ONE MONOMER HAVING THE FORMULA

United States Patent [1 1 Fock et a1.

[ Jan.8,1974

[ METHOD OF TREATING A WOOD SURFACE WITH LINEAR HEAT-HARDENABLE COPOLYMERIZATE [75] Inventors: Jiirgen Fock, Essen-Bredeney;

Ulrich Holtschmidt, Essen, both of [2]] App]. No.: 190,397

Related U.S. Application Data [62] Division of Ser. No. 31,748, April 24, 1970, Pat. No.

[30] Foreign Application Priority Data May 6, 1969 Germany 1922942 [52] U.S. Cl. 156/334, 161/250 [51] Int. Cl. C09j 7/02, B32b 27/10 [58] Field of Search 156/334, 332, 330

[56] References Cited UNITED STATES PATENTS 3,607,615 9/1971 Hatakeyama 161/218 3,563,953 2/1971 Lehmann et a1 260/63 3,242,123 3/1966 Mayfield et al 260/296 3,553,153 1/1971 Hazen et a1 260/296 Primary Examiner-Douglas J. Drummond Assistant Examiner-M. G. Wityslhyn Att0rney.lames E. Bryan 57 ABSTRACT This invention relates to a linear heat-hardenable copolymerizate, and to a method of treating a wood surface with a foil of the said copolymerizate, the copolymerizate having a limiting viscosity of r; 0.7 to 3.0 (100 ml g) measured in toluene at 20 C., and comprising 70 to 94 mole percent of a compound selected from the group consisting of styrene or at least one monomer having the formula in which R is selected from the group consisting of hydrogen and a methyl group, and R is an alkyl group having one 'to four carbon atoms, 2 to 15 mole percent of at least one compound selected from the group consisting of maleic anhydride and itaconic acid anhydride, and

4 to 15 mole percent of at least one compound selected from the group consisting of acrylic acid glycidyl ester and methacrylic acid glycidyl ester.

2 Claims, No Drawings This is a division of application Ser. No. 3 l ,748, filed Apr. 24, 1970 now U.S. Pat. No. 3,694,418.

This invention relates to novel linear heat-hardenable copolymerizates and to the use thereof, preferably in the form of selfsupporting foils, for improving the surfaces of raw materials, particularly sheets of wood, by pressing the foils thereon at elevated temperatures.

Known to the art are various linear copolymerizates containing reactive groups which are cross-linked at elevated temperatures with conversion of the thermoplastic copolymerizate into an insoluble and infusible polymerizate.

U. S. Pat. No. 2,604,463, for example, describes a linear thermoplastic copolymerizate obtained from acrylic acid glycidylester, acrylic acid, styrene, and acrylic acid methyl ester. The acrylic acid glycidyl ester and the acrylic acid are present together in the I copolymerizate in a quantity such that, when the copolymerizate is heated, a sufficient cross-linking occurs. The quantity of the two aforementioned compounds should not, however, exceed 20 percent by weight, based upon the weight of the copolymerizate.

French Pat. No. 1,374,297, discloses the preparation of copolymerizates of styrene, ethyl acrylate, acrylic acid, and acrylic acid glycidyl ester in the form of an emulsion. Formed during the reaction are lattices which can be cross-linked after application and drying at temperatures in the range of 100 to 150 C.

U. S. Pat. No. 3,223,670, discloses copolymerizates of vinyl acetate, acrylic acid, itaconic acid, and acrylic acid glycidyl ester. These copolymerizates also are obtained by emulsion polymerization at temperatures in the range of 55 to 60 C.

U. S. Pat. No. 3,242,931, discloses the preparation of an adhesive for plywood consisting of a heathardenable copolymerizate obtained, for instance, by emulsion polymerization of vinyl acetate, methacrylic acid glycidyl ester, and acrylic acid. A thickening agent is added to the resulting emulsion.

British Pat. No. 1,025,694, similarly discloses hardenable copolymerizates of acrylic acid ethyl ester, methacrylic acid glycidyl ester, and acrylic acid. It is disclosed in the patent that these products are well suited for the treatment of surfaces.

The hardenable copolymerizates of the prior art are employed essentially as binding agents for stoving lacquers. Selfsupporting foils based on such products, which would be suitable for the pressure coating of wood sheets, are not described. Actually, they would not have been considered for such use because of the hardenable conditions thereof, since the residence time within the heated mold of the materials to be improved would have to be so long as to be prohibitive. This is undesirable not only in view of the long time required, but because it may result in damage to delicate materials, such as wood sheets, which might be damaged either mechanically or chemically by prolonged residence in the mold while subjected to pressure and.

an elevated temperature.

The present invention provides linear heathardenable copolymerizates having relatively short hardening times yet possessing sufficient rheological properties to form pore-free and] flawless surface protective layers at moderate pressure, particularly on sheets of wood materials, which protective layers moreover adhere well to such wood bases.

The copolymerizates of the present invention contain to mole percent of styrene or one or more monomers having the formula wherein R, is hydrogen or a methyl group, and R is an alkyl group having from one to four carbon atoms,

2 to 15 mole percent of maleic anhydride and/or itaconic acid anhydride, and

4 to 15 mole percent of acrylic acid glycidyl ester and/or methacrylic acid glycidyl ester. The copolymerizate also may contain 0 to 3 mole percent of vinyl pyridine. The copolymerizate has a limiting viscosity ofn 0.7 to 3.0 ml g measured in toluene at 20 C.

The structure of the copolymerizate may be recognized from essentially three specific types of monomers, i.e.:

1. Present in an excess amount, based upon the weight of the copolymerizate, is a carrier monomer or a mixture of several carrier monomers. These carrier monomers are either alkyl esters or acrylic acid or methacrylic acid, wherein the alkyl residue of the alcohol employed for the esterification has from one to four carbon atoms, or mixtures of such acrylic acid and methacrylic acid esters or, instead of these esters, styrene may be employed.

Exemplary of the acrylic acid and methacrylic acid esters are methyl esters, ethyl esters, propyl esters, and butyl esters.

2. Smaller portions of maleic anhydride and/or itaconic acid anhydride, as compared to the carrier monomer. The use of unsaturated cyclic dicarboxylic acid anhydrides as compounds capable of reacting with glycidyl groups constitutes an essential part of the present invention since these anhydrides effect the rapid hardening of the copolymerizates and thereby render them useable for the intended application.

3. Acrylic and/or methacrylic acid glycidyl esters are employed as monomers containing glycidyl groups.

It is possible to employ, as a fourth polymerization component, vinyl pyridine in small quantities; it catalyzes the hardening process because of its basic proper ties and is built into the polymerizate by means of its vinyl group.

Since the copolymerizates are designed particularly for improving the surfaces of materials made from wood, it is necessary that the copolymerizates, during heating thereof under pressure and prior to being completely hardened, have a sufficient rheological capacity in order, on one hand, to become adequately bonded to the base while simultaneously forming a sealed surface, on the other hand. For this purpose, it is necessary that the copolymerizates not exceed a specific molecu' lar weight. The novel linear heat-hardenable copolymerizates have, therefore, a limiting viscosity characterizing the molecular weight (Staudinger index of 0.7 to 3.0), measured in toluene at 20 C.

Self-supporting foils made from the novel copolymerizates can be stored for a practically unlimited time at normal temperatures. Yet, even under unfavorable conditions, for example when exposed to elevated temperatures during storage, the foils may be stored for a length of time corresponding to the consumption thereof.

In the course of the hardening of the linear copolymerizates at elevated temperatures, the carboxylic acid anhydride groups contained in the polymerizate react with the glycidyl groups with the formation of a three-dimensional reticular structure. This crosslinking reaction can be illustrated in a simplified manner as follows:

. CHg-CHT(EHCH In this general structure, T signifies the carrier monomer.

The preparation of the linear heat-hardenable copolymerizate is effected in known manner, while care must be taken to ensure that no cross-linking or at least no significant cross-linking occurs during the copolymerization. For this reason, two polymerization processes have been found to be useful:

a. Particularly advantageous is emulsion polymerization at low temperatures, particularly in the range of 0 to 20 C. For the purpose of preparing the emulsion, it is possible to employ conventional emulsifiers among which the following are exemplary: sodium lauryl sulfate, sodium dodecyl diphenyl sulfonate, polyethylene glycol isooctyl phenyl ether, sodium alkyl acrylic polyether sulfonate, sodium tetra-N-l (1,2-dicarboxyethyl)-N-octadecyl sulfosuccinate, polyethylene glycol nonylphenyl ether, and polyethylene glycol tridecyl alcohol ether.

The emulsion polymerization may be performed at controlled pH values, and sodium acetate, sodium hydrogen phosphate and sodium oxalate are particularly suitable as buffer salts.

Usable as redox-initiating systems are preferably peroxides and hydroperoxides in combination with iron (ID-salts, ascorbic acid, and sodium formaldehyde sulfoxylate. The bivalent iron also may be employed in the form of the ethylene diamine tetraacetic acid complex. An especially suitable peroxide is cumene hydroperoxide.

In connection with the determination of the quantities of unsaturated monomeric compounds required for the preparation of the copolymerizate, it should be taken into account that, on the basis of the varying reactivity and reaction velocity, the quantities of the reactants in the reaction do not correspond exactly to the quantities of the different compounds contained in the polymerizate. The amounts to be employed are best determined on the basis of a preliminary test.

The emulsion polymerization preferably is carried out in the following manner:

The emulsifier, dissolved in water, is added to water which is free from oxygen as much as possible. While stirring, cooling is effected to -5 to C., preferably 0 C., and the reduced portion of the initiator, the buffer, and the entire monomeric mixture are then added, whereby a pH value between 3 and 5 will result. Then, the peroxide, which previously was dissolved in a small amount of carrier monomer, is added. Until complete conversion is attained, stirring is effected in an atmosphere of nitrogen. After completion of the reaction, the polymerizate is precipitated from the emulsion with an excess of methanol. The reaction mixture is washed with water and the remaining water is removed insofar as possible by means of a filter press. The reaction product thus obtained is then incorporated into various organic solvents and may be poured out to films which harden completely at temperatures between and 150 C. under pressure.

b. The polymerization of the monomers in solvents renders possible the use of somewhat higher temperatures so that working can be effected at temperatures in the range of about 20 to 80 C. The solvent and the diluent both should have the capacity for dissolving the resulting polymerizate. Exemplary of such solvents are: dioxane, methylene chloride, acetone, and mixtures of methylethyl ketone or isopropyl alcohol with toluene. Generally speaking, the weight ratio of the polymerizable monomers to the solvent should be approximately 3 to 4: l. The known polymerization initiators, such as, for example, azodiisobutyric acid nitrile, benzoyl peroxide, cumene hydroperoxide, or cumene peroxide may be employed in a quantity of about 0.5 percent by weight, based upon the weight of the monomer.

When foils are made from the novel linear heathardenable copolymerizates, for example by dissolving the copolymerizates in a suitable solvent, casting the same and allowing the solvent to evaporate, transparent products are obtained which are well suited to being further treated and which, when pressed upon wood, for example at a temperature in the range of to 160 C preferably C. and at a pressure of about 25 kg/cm yield hard, well adhering, completely transparent films which are resistant to dilute acids and alkalies, as well as alcohol and benzine. The films do not swell, or swell only negligibly, under the action of chlorinated solvents.

The invention will be further illustrated by reference to the following examples in which all parts are parts by weight.

XAM E r.

solved in 5 parts of oxygen-free water) and 0.28 part of rene). During reactiom th e temperature is constantly maintained at C. After 40 hours, the emulsion is introduced into 750 parts of methanol; the precipitated polymerizate is washed with water, again introduced EXAMPLE 3 Following the procedure of Example 1, a series of experiments is performed in which varying quantities of maleic anhydride and acrylic acid glycidyl ester are emdisplay the brown coloration mentioned in connection with Example 1. The Buchholz hardness (DIN 53153) into 750 parts of methanol, and then filtered in a filter ployecL Styrene is replaced by methacrylic acid ethyl press. The yield amounts to 95 percent of theoretical. ester and Sodium acetate is replaced by disodium The polymerizate issoluble in benzene, toluene, methdrogn phosphate Al l l ketone and ilti l d The following table shows the content of maleic anfuran' The staufllmger ,mdex m P at Q 1S 77: hydride and acrylic acid glycidyl ester in the mono- (100 m1 g anhdrfde and glycldyl groups. meric mixture; the reaction duration, the conversion, are proven to be pre sen t quahtatlvelx by A Spec the Staudinger index in xylene, the swelling index after troscopy andquantitatively by titrat on with KOI-I an heating at 180 C. for 10 minutes, as well as the gel con- HCl, respect1vely. The acid anhydride content 1s 3.3 tent after Crosshnking Maleic Anhydride Acrylic acid Duration reaction Conversion (100 ml g") Swelling index gel content glycidyl ester according to Danncnberg Mole Mole h (C.)

5 5 4 as 1.52 2.50 99 5 10 4.5 93 1.40 1.95 99 5 15 4.5 95 1.03 1.90 100 10 s 5 93 1.25 2.25 91 10 10 4.5 90 1.20 1.80 99 15 5 4.5 83 1.01 2.40 92 15 10 4.5 85 0.88 2.10 98 percent by weight, and the glycidyl content is 8:7 per- As des cribed in Example 1, the films are pressed; cent by weight. The initial conversion velocity of the they are transparent, hard, and show no tension-fissure polymerization amounts to 15% h". corrosion after a prolonged treatment with methanol; A film pressed upon wood at a temperature of 140 they are not affected by dilute acids and alkalies. The C. for 15 minutes atapressure of kg/cm is transpar swelling in methylene chloride and ethyl acetate deent, has a Buchholz hardness (DIN 53153) of 100 and creases with an increasing content of acrylic acid glyciis of a light brown color. The adhesiveness is excellent. dyl ester. Corrosion due to a tension-fissure formation after the action of either methanol or ethanol-water mixtures EXAMPLE 4 does not occur. The hardened film is resistant to dilute 1 0 parts of oxygen-free water are cooled to 0 C acid and alkalies, alcohol and benzine. Only a moder and added thereto are 5 parts of p-ter.-octyl phenoxy ate swelling occurs after a 24-hour treatment withpolyethylene glycol ether, parts of methacrylic acid methylene chloride or ethyl acetate. Film samples were methyl ester, 4 parts of acrylic acid glycidyl ester, and heated for 10 minutes at 150 C. and thereafter treated 6.1 parts of maleic anhydride. The mixture is homogewith boiling chloroform: the gel content was found to 40 nized and then added thereto, drop by drop, are 3 parts be 100 percent. The swelling index according to H; of disodium hydrogen phosphate, 1.2 parts of iron (II)- Dannenberg and W. R. Harp, .lr., Anal. Chem. 28 ammonium sulfate (dissolved in 5 parts of oxygen-free (1956) 86 (determined after standing for 24 hours in water) and 0.28 part of cumene hydroperoxide (disa 1,2-dich1oroethane atmosphere) is 2.1. A film kept solved in 2 parts of methacrylic acid methyl ester). The for 3 months at room temperature is actually slightly conversion after 6 hours is 93 percent of theoretical. cross-linked but, during pressing, still displays a good; The Staudinger index in chloroform at 20 C. is 1 1.5 rheological capacity. (100 ml g). The initial conversion velocity is 150% h. The swelling index is 1.9 at 150 C. and 10 min- EXAMPLE 2 utes time. The gel content is 99 percent. The acid anhy- The procedure of Example 1 is repeated except that dride content is Percent y Weight, the glycidyl employed in the place of iron (ID-ammonium sulfate is l" is P by Weight Th IR Spectrum 1S1 ya mixture of 0.1 part of sodium formaldehyde sulfoxydude and glycldy] groups Posltlve late, 0.015 part of ethylene diamine tetraacetic acid Films Pressed p Wood at a Emperature of 5 and 0 75 pan f iron ch1oride hydrate The yield for 10 minutes are transparent, hard, excellent with reafter 24 hours is 90 percent of theoretical. The initial Spect to the adheslveness thereof have a Buchholz conversion velocity is 175% The Staudinger hardness (DIN 53153) of 110, and are not affected by index i toluene at 20 C is h 23 00 ml The dilute acids and alkalies. After the action of methylene swelling index is 1.7 at a temperature of 150 c. and 10 chloride and ethyl acetate, a Slight Swelling Occurs after minutes time. The gel content is 100 percent. The acid 24 hours; test benliue as no adverse effect. A film anhydride and glycidyl group content is 3.4 percent by S 3 months 15 Still Capable of flowmg dufmg weight and 8.8 percent by weight, respectively. Also Pressmg proven by the IR spectrum, aside from the anhydride EXAMPLE 5 and glycidyl groups, is a higher proportion of carboxylic acid groups. A film pressed upon wood does not The Procedure of Example 4 above 15 repeated but employed instead of 40 parts of methacrylic acid methyl ester is a mixture of 20 parts of. methacrylic acid methyl ester and 20 parts of methacrylic acid-n-butyl ester. Further, only 3.05 parts of maleic anhydride are used. The conversion after 8 hours is 94 percent of theoretical. The Staudinger index in chloroform at 20 C. is 17 2.05 (100 ml g). The initial conversion velocity is 165% h'. The swelling index at 150 C. and 10 minutes time is 2.1. The gel content is 100 percent. The acid anhydride content is 2.8 percent by weight, and the glycidyl content is 7.4 percent by weight.

Films pressed upon wood at a temperature of 145 C. for 10 minutes are transparent, hard, excellent with respect to adhesiveness thereof, have a Buchholz hardness (DIN 53153) of 95, and are not affected by dilute acids and alkalies. Methylene chloride and ethyl acetate swell them only to a minor extent; test benzine has no adverse effect. No tension-fissure corrosion after the action of methanol or ethanol-water mixtures is noted. A film stored for 3 months is still capable of flowing during pressing.

EXAMPLE 6 The procedure of Example 4 is followed with the further addition, however, to the monomeric mixture of 1.8 parts of vinyl pyridine. The conversion after 5 hours is 93 percent. The initial conversion velocity is 160% h. The Staudinger index in chloroform at 20 C. is 1 0.95. The swelling index is 1.9 at a temperature of 150 C. and minutes time. The gel content is 100 percent. The acid anhydride content is 2.9 percent by weight, and the glycidyl content is 7.5 percent by weight. The IR spectrum shows anhydride and glycidyl groups positive.

Films pressed upon wood at a temerature of 145 C. for 10 minutes are transparent, hard, excellent with respect to the adhesiveness thereof, have a Buchholz hardness (DIN 53153) of 115, and are not affected by dilute acids and alkalies. After the action of methylene chloride and ethyl acetate, only a minor amount of swelling occurs after 24 hours; test benzine has no adverse effect.

EXAMPLE 7 Added to 100 parts of oxygen-free water at a temperature of 0 C. are 6 parts of sodium lauryl sulfate (dissolved in parts of oxygen-free water), 50 parts of methacrylic acid butyl ester, 5 parts of acrylic acid glycidyl ester and 5 parts of itaconic acid anhydride. The mixture is homogenized and then added thereto, drop by drop, are 3 parts of disodium hydrogen phosphate, 1.2 parts of iron (ID-ammonium sulfate (dissolved in 5 parts of oxygen-free water), and 0.28 part of cumene hydroperoxide (dissolved in 2 parts of methacrylic acid butyl ester). The conversion after 8 hours is 90 percent of theoretical. The initial conversion velocity is 140% h. The Staudinger index in chloroform at 20 C. is 1 0.90. The swelling index is 2.5 at 150 C. and 10 minutes time. The gel content is 96 percent. The acid anhydride content is 5.8 percent by weight, and the glycidyl content is 7.8 percent by weight. The IR spectrum shows: anhydride and glycidyl groups positive.

Foils pressed upon wood at a temperature of 145 C. for 10 minutes are transparent, medium hard, well adhesive, have a Buchholz hardness (DIN 53153) of 80, and are not affected by dilute acids and alkalies. After the action of methylene chloride, ethanol, acetone and ethyl acetate, a very small swelling occurs after 24 hours; test benzine has no adverse effect. The foil is resistant against tension-fissure corrosion.

EXAMPLE 8 Added to parts of oxygen-free water at a temperature of 0 C. are 5 parts of p-tert.-octyl phenoxy polyethylene glycol ether (dissolved in 20 parts of oxygenfree water), 20 parts of methyl methacrylate, 20 parts of ethyl acrylate, 4 parts of glycidyl acrylate, and 6.1 parts of maleic anhydride. The mixture is homogenized and then added thereto, drop by drop, are 3 parts of disodium hydrogen phosphate, l.2 parts of iron (11)- ammonium sulfate and 0.28 part of cumene hydroperoxide (dissolved in 2 parts of methyl methacrylate). The conversion after 8 hours is 90 percent of theoretical. The initial conversion velocity is h. The Staudinger index in toluene at 20 C. is 1 1.02. The swelling index is 2.9 at C. and 10 minutes time. The gel content is 98 percent. The acid anhydride content is 3.3 percent by weight and the glycidyl content is 8.0 percent by weight. The IR spectrum shows: anhy-' dride and glycidyl groups positive.

Foils pressed upon wood at a temperature of 145 C. for 10 minutes are transparent, well adhesive, have a Buchholz hardness of 90, and are not affected by dilute acids and alkalies. Acetone, ethyl acetate and ethanol swell them only very slightly after a 24-hour treatment.

EXAMPLE 9 200 parts of dioxane are freed from dissolved oxygen by boiling at reflux under nitrogen. Then added are 33.2 parts of methyl methacrylate, 10.7 parts of itaconic acid anhydride, and 6.1 parts of glycidyl acrylate. The batch is stirred at a temperature of 20 C. under nitrogen; initially added are 0.25 part and after 2, 4, 6, and 8 hours, 0.05 part of azo-diiso-butyric acid nitrile (each 0.05 part being dissolved in 2 ml of methylene chloride). The conversion after 67 hours is 92 percent of theoretical. The Staudinger index in tetrahydrofuran at 20 C. is 17 0.5. The swelling index is 1.0 at 150 C. for 10 minutes time. The gel content is 99 percent. The acid anhydride content is 9.8 percent by weight and the glycidyl content is 13.8 percent by weight. The IR spectrum shows: anhydride and glycidyl groups positive.

Foils pressed upon wood at a temperature of 145 C. for 10 minutes are transparent, well adhesive, have a Buchholz hardness (DIN 53153) of 115, and are unaffected by dilute acids and alkalies, by test benzine and ethanol. Methylene chloride, ethyl acetate and acetone cause only slight swelling after a 24 hour treatment.

H EXAMPLE 10 Added to 200 parts of oxygen-free methylene chloride are 33.2 parts of methyl methacrylate, 4.6 parts of maleic anhydride, and 12.2 parts of glycidyl acrylate. Thereafter, stirring is effected under nitrogen at 40 C and then added are initially 0.25 part, and therafter, after 2, 4, 6 and 17 hours, a 0.05 part quantity of azoaiisobutyric acid nitrile. The conversion after 80 hours is 86 percent of theoretical. The Staudinger index in tetrahydrofuran at 20 C. is 1 0.62. The swelling index is 1.9 at 150 C. and 10 minutes time. The gel content is 98 percent. The acid anhydride content is 2.6 percent by weight and the glycidyl content is 19.3

percent by weight. The IR spectrum shows: anhydride and glycidyl groups positive.

Foils pressed upon wood at a temperature of 145 C. for 10 minutes are transparent, adhesive, have a Buchholz hardness (DIN 53153) of 1 10, and are unaffected by dilute acids and alkalies. Methylene chloride, ethyl acetate and acetone cause only minor swelling after a 24-hour treatment.

It will be obvious to those skilled in the art that many modifications may be made within the scope of the present invention without departing from the spirit thereof, and the invention includes all such modifications.

What is claimed is:

l. A method of treating a wood surface which comprises disposing on said wood surface a single layer of foil of a linear heat-hardenable copolymerizate, comprising;

70 to 94 mole percent of a compound selected from the group consisting of styrene or at least one monomer having the formula:

in which R is selected from the group consisting of hydrogen and a methyl group and at least 50 percent of said R, groups is methyl, and R is an alkyl group having one to four carbon atoms,

2 to 15 mole percent of at least one compound selected from the group consisting of maleic anhydride and itaconic acid anhydride, and 4 to 15 mole percent of at least one compound selected from the group consisting of acrylic acid glycidyl ester and methacrylic acid glycidyl ester, said copolymerizate having a limiting viscosity of 1 0.7 to 3.0 ml g) measured in toluene at 20C; and pressing said foil onto said wood surface at a pressure in the range of about 15 to 40 kg/cm and at a temperature in the range of about to C to substantially complete the cross-linking of said foil material and form a nontacky, hard, abrasionresistant coating on said wood surface.

2. A method according to claim 1 in which the copolymerizate includes, in addition, not in excess of 3 mole percent of vinyl pyridine. 

2. A method according to claim 1 in which the copolymerizate includes, in addition, not in excess of 3 mole percent of vinyl pyridine. 